We report here the combined use of computational chemistry and low-temperature NMR spectroscopy to probe the mechanism of a highly stereoselective glycosylation reaction employing 2,3-anhydrofuranosyl glycosyl sulfoxides (2 and 4). The reaction involves a two-step process that is carried out in one pot. In the first step, the sulfoxide is reacted with triflic anhydride leading to the formation of a single intermediate. Using NMR spectroscopy, we have established the structure of this intermediate as a glycosyl triflate. In the second step, the acceptor alcohol is added to the reaction mixture, which leads to the highly stereocontrolled formation of the glycoside product. The structure of the major product is consistent with a pathway involving an S(N)2-like displacement of the triflate by the alcohol. In the predominant intermediate that is formed, there is a trans relationship between the triflate group and epoxide. Therefore, in the glycoside product there is a cis relationship between the epoxide and the aglycone. In addition to providing insight into these reaction pathways, these investigations have also allowed us to identify conditions under which the glycosylations can be made to proceed with even greater stereoselectivity and in higher yield.